Light-sensitive metal base photographic element



Nov. 16, 1954 G. F. NADEAU ErAL 2,694,639

LIGHT-SENSITIVE METAL BASE PHOTOGRAPHIC ELEMENT Filed June 14, 1951 14GELA r//v EMULS/olv 13 GELA TIN F19. 1 ,z Pom/Nn Acer/1TE- CELLULOSENITRATE ,o cAReoxYLATEo coPoLYMER RESIN-POLYvl/VYL ACETATE- TITANIUMox/DE METAL SUPPORT Ta foLYv/NYL ALCOHOL EMULS/olv 1716 PoLYv/NYLALcoHoL Fg- 2 '5E- \HYDROLYZED POLYVNYL ACETATE 9\\\\\\\\\\\\\\\\\`\\\\CELL ULOSE NITRATE l0 '9 TA /oN F193 l? HYDRO/.HE D 10 CELLULOSE ACETATEGale ENade au Clemens. Sieg/'0k Carl E Smzh JNVENToRs BYO-al' 2,694,639Patented Nov. 16, 1954 LIGHT-SENSITIVE METAL BASE PHOTOGRAPHIC ELEMENTGale F. Nadeau, Clemens B. Starck, and Carl F. Smith,

Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y.,a corporation of New Jersey Application June 14, 1951, Serial No.231,632

Claims. (Cl. 95-8) This invention relates to light-sensitivephotographic elements and more particularly to such elements having ametallic base or support.

In the art of photography, it is well known that the conventionalhydrophilic colloid-silver halide emulsion layers require a support suchas cellulose ester, resin, paper, metal, etc. Many patents directed tomeans for adhering the emulsions to such supports have been grantedmainly in the field of adhering emulsions to cellulose ester and resinsupports.

The prior art would indicate that relatively few problems have arisenwhen the emulsion is to be adhered to metallic supports. However, wehave discovered that in order to obtain optimum adherence and quality inmetalbased sensitive elements, it is essential to provide certainadhesive or subbing layers for obtaining the desired adherence of theemulsion to the metal support. This is particularly true when thesensitive elements are to be subjected to abnormal atmosphericconditions such as high temperature and low relative humidity, withconditions are manifest by the formation of fissures in the emulsionlayer.

Accordingly, the primary object of our invention is to provide subbinglayers for adhering hydrophilic colloid-silver halide emulsion layers tometal supports. Other objects will become apparent from consideration ofthe following description of our invention.

In general, the objects of our invention are accomplished by providing ametal base or support, such as aluminum, steel, copper, brass, etc.,particularly in the form of thin sheets, with two thin subbing layers,the rst comprising a mixture of a light-colored inert filler material, aresinous copolymer, and preferably, but not necessarily, polyvinylacetate, the second layer being a mixture of polyvinyl acetate andcellulose nitrate. Thus provided with a subbed metal-based element, thedesired hydrophilic colloid-silver halide emulsion layer may then beadhered thereto by means of one or more additional organic colloidsubbing layers containing polymeric units in common with the colloidvehicle comprising the particular hydrophilic organic colloid-silverhalide emulsion y vehicle under consideration.

In the drawings:

Fig. l shows in greatly enlarged cross-sectional view the appearance ofmetal-based photographic element carrying a gelatino-silver halideemulsion layer adhered to the metal base by means of the subbing layersof the invention.

Fig. 2 is a similar View of a metal-based element carrying a polyvinylalcohol-silver halide emulsion layer adhered to the base by means of thenovel subbing layers.

Fig. 3 is a similar view of a metal-base lm utilizing the subbing layersof the invention for causing adherence of a cellulose acetate-silverhalide emulsion to the metal support.

The following examples illustrate preferred methods for adheringhydrophilic organic-colloid-silver halide emulsion layers to metalsupports:

Example 1 Per cent Acetone Butyl acetate In this subbing composition thesolvents may be replaced by a comparable amount of methylene chloride,but the indicated solvent combination is preferred. In the compositionthe ratio of the two resins may be varied somewhat, but approximatelyequal parts by Weight of the two resins are preferred. However, asperviously mentioned, this composition can include only the solidingredients: resinous copolymer and filler material. The polyvinylacetate is not an essential ingredient, serving only asa modifier orplasticizer. The essence of the invention is the use of thecopolymer'and tiller material as the first subbing layer 11 inconjunction with the second subbing layer 12 of polyvinyl acetate andcellulose nitrate to be described hereinafter. The filler material,titanium oxide, can be varied within reason, a range of from about 25 to75 per cent by weight of the resins of the filler material being mostefficacious. The filler material, titanium oxide, is representative of aclass of light-colored inert materials such as barium sulfate, calciumcarbonate, zinc oxide, etc., essential to successful operation of ourinvention. That is, it has been found that while useful products can bemade when the filler material is omitted from the subbing formula, thefiller material, when used in conjunction with the resinous vehicle, notonly provides a white or light-colored background for silver imagesdeveloped on the metal support, but, which is more important, preventsow of the subbing layers during drying and shrinking of the emulsion,thus preventing the emulsion from showing shrinkage cracks or skidding.In the formula the viscosity of the particular polyvinyl acetate used isnot especially critical as it appears only to alter the viscosity of thesubbing composition.

The resinous copolymer indicated in the subbing formula is acarboxylated copolymer of a mixture of vinyl chloride, vinyl acetate,and an ,-ethylenically unsaturated dicarboxylic acid, such as fumarie ormaleic acid, preferably one containing about 86 per cent by weight ofvinyl chloride groups, about 13 per cent by weight of vinyl acetategroups, and about l per cent by weight of maleic acid groups. In thevarious iigures of the drawings is shown the position of the subbinglayer 11 atlig'tnedi to the metal support 10 by the method just de- SCIle The first subbing layer 11 s then coated with the second thin subbinglayer from the following representative composition:

Per cent Cellulose nitrate 3 Polyvinyl acetate 0.5 Titanium oxide 2.5Acetone 40 Ethylene glycol monomethyl ether 10 Methyl alcohol 44 In thevarious figures of the drawings this subbing layer is represented bylayer 12.

ln the subbing formula immediately above, the ller material may beomitted, but its presence tends to improve the appearance of thecoating. The type of cellulose nitrate used is not especially critical,but it is preferable to use the well known low to medium viscosityhighly alcohol-soluble varietyl containing about ll per cent nitrogen.The proportions of polyvinyl acetate and cellulose nitrate in theformula may be varied somewhat, the preferred proportions being fromabout six to twelve parts of cellulose nitrate per part of polyvinylacetate.

As pointed out above, the metal support, now having been provided withthe two subbing layers of the invention, can be sensitized with avariety of organic hydrophilic colloid-silver halide emulsions. This isaccomplished by utilizing a third intervening subbing layer havingapproximately the same chemical and physical characteristics as thecolloid vehicle of the emulsion layer.

Accordingly, 'agelatino silver halide emulsion is applied to the elementprovided with subbing layers 11 and 12 as follows:

A third thin subbing'layer 13 was applied to the surface -of sub-hingvlayer u12 `from the composition:

Per cent Gelatin 1.2 Methyl alcohol `87.8 Water '10 Glacial acetic acid1.0

in whichthe :gelatin concentration maybe varied as desired, for example,between l and 2 per vcent `concentration. Following this, lagelatine-silver halide 'emulsion layer 14 of vthe conventional type wasA'coated 'over subbing layer .13. The result was a dilm of .goodflexibility free of the .mentioned defects. As will be apparent,suitable antihalation materials, for example, dyes, may :be incorporatedinto the sensitive llm as desired.

Example 2 Per cent Hydrolyzed polyvinyl acetate .1.5 Cellulose nitrate.`0.5 Ethylene -glycol monomethyl ether l5 Methyl alcohol 75 Water 8 In.this formula the .ratio Vo'f partially r`hydrolyzed polyvinyl `acetateto cellulose nitrate can be varied somewhat, for example, within'therange'of 4from about two to six parts per'part of cellulose nitrate. Thehydrolyzed polyvinyl yacetate used :in the "above formula 'contained37.9% vinyl acetate groups by weight, the remainder being vinyl alcoholgroups. While a hydrolyzed polyvinyl acetate of this analysis ispreferred, other hydrolyzed polyvinyl acetates varying as much as 10 percent .in vinyl alcohol `group content can tbe used for .thesamepurpo'se.

Per cent Polyvinyl alcohol 1.5 Methyl alcohol '40 Zirconium nitrate(based on weight of lpolyvinyl alcohol) Water 54 Following application.of subbing layer 16, a polyvinyl alcohol-silver halide emulsion layerI7 is coated in a well known manner to provide the Vfinishedproductshown in Fig. 2 of the drawings.

Example 3 The pre-subbed element prepared as described in Bxample 1 andhaving subbing layers 11 and 12 of thefinvention on the metal supportv10, layer .11 preferably containing the modifier resin polyvinylacetate, "is fcoated as shown in Fig. 3 with a subbing layer 18 from thecomposition .Per cent Hydrolyzed cellulose ester 1-3 Water 10 Ethyleneglycol monomethyl ether l5 Methyl alcohol 74 The .hydrolyzed celluloseester used in the above lcornposition is selected from hydrolyzedcellulose esters containing from about 19 to 33% acyl groups, andpreferably consists of hydrolyzed cellulose acetate containing about 27%acetyl. Hydrolyzed cellulose esters' described iu the Salo U. S. Patent2,110,491 granted March 8, 1938, are suitable for this composition andfor the Vcolloid vehicle of the silver halide emulsion layer 19 which issubsequently applied over layer 18. 'The cellulose ester emulsion layercan be applied from solvent systems selected from those disclosed in the'patent mentioned.

We claim:

l. A light-sensitive photographic element comprising a metal support,adhered directly thereto, a first layer of a mixture of a light-coloredinert filler material and a resinous copolymer of a mixture of vinylchloride, vinyl 4 acetate and an ,-ethylenically unsaturateddicarboxylic acid, 'said 'layer -'being l'substantially free 'ofpolymerizable material adhered directly to said first layer a secondlayer of a mixture of polyvinyl acetate and cellulose nitrate, and ahydrophilic organic colloid-silver halide emulsion layer adhered to saidsecond layer.

2. A light-sensitive photographic element comprising a metal support,adhered directly thereto, a'first layer of a mixture of a light-colored4inert filler material, polyvinyl acetate and a resinous copolymer ofvinyl chloride, vinyl acetate `and an rogt-ethylenically unsaturateddicarboxylic acid, said layer being substantially free of p'olymerizablematerial, .adhered directly to said first .layer a second layer of amixture of polyvinyl acetate and cellulose nitrate, and a hydrophiliccolloid-silver halide emulsion layer adhered to .said second layer.

3. A light-sensitive photographic element comprising a metal support,adhered directly thereto, a first layer of amxture ofa light-coloredinert filler material, 'polyvinyl acetate and .a resinous `copolymercontaining about 86% by weight of vinyl chloride groups, about 13% byweight of 'vinyl acetate groups, 'and about 1% by weight of maleic acidgroups, said layer being substantially free of polymerizable material,adhered directly to said first layer 'a second llayer of a mixture 'ofpolyvinyl acetate and cellulose nitrate, and a hydrophilic 4organiccolloid-silver halide emulsion layer adhered to said second layer.

4. A light-sensitive photographic element comprising 'a metal support,adhered directly thereto, a first layer of a mixture of a light-coloredYinert filler material, polyvinyl acetate and a resinous 4copolymercontaining about 86% by weight of vinyl chloride groups, about 13% byweight of Vinyl acetate groups, and labout 1% by weight of vmaleic acidgroups, lsaid layer being substantially free of `polymerizable material,adhered directly to ysaid first layer aisecond layer of a ymixture ofpolyvinyl acetate vand cellulose nitrate, and a gelatine-silver halideemulsion adhered Eto said 'second layer by means of a gelatin layer.

5. .A ,light-'sensitive .photographic yelement comprising a metalsupport, adhered directly thereto, a yfirst layer o'f a mixture of alight-colored :inert filler material, polyvinyl acetate and a resinouscopolymer containing about 86% by weight of vinyl chloride groups',about 13% yby weight of vinyl acetate groups, and about 1% by weight ofmaleic acid groups, said layer being substantially free of-polymerizable material, adhered directly to said first layer a secondlayer of a mixture of polyvinyl acetate and cellulose nitrate and apolyvinyl alcohol-silver halide emulsion layer adhered to said secondlayer by means of a layer of partially hydrolyzed polyvinyl acetate.

6. A light-sensitive photographic element comprising a metal support,adhered directly thereto, a first layer of a mixture of a light-coloredinert filler material, polyvinyl acetate and a resinous copolymercontaining about 86% by weight of vinyl chloride groups, about 13% byweight of vinyl acetate groups, and about 1% by weight of maleic acidgroups, said layer being substantially free of polymerizable material,adhered directly to said first layer a second .layer of a mixture ofpolyvinyl acetate and cellulose nitrate, and a hydrophilic celluloseorganic acid ester-silver halide emulsion layer adhered to said secondlayer by means of a hydrophilic cellulose ester layer.

7. A light-sensitive photographic element comprising a metal support,adhered directly thereto, a first layer of va mixture of approximatelyequal parts by weight of polyvinyl acetate and a resinous copolymercontaining about 86% by weight of vinyl chloride groups, about 13% byweight of vinyl acetate groups and about 1% by weight of maleic acidgroups together with from about 25-75% by weight of resin of alight-colored inert filler material, 'said layer being substantiallyfree of polymerizable material, adhered directly to said first layer asecond layer of a mixture of from about 6 to l2 parts of cellulosenitrate per part of polyvinyl acetate, and a gelatino-silver halideemulsion layer adhered to said second layer by means of a gelatin layer.

8. A light-sensitive photographic element comprising an aluminumsupport, adhered directly thereto, a first layer of a mixture ofapproximately equal parts by weight of polyvinyl acetate and a resinouscopolymer containing about 86% by weight of vinyl chloride groups, about13% Vby weight of vinyl acetate groups and about 1% by weight of maleicacid groups, together with from about 25-75% by weight of resin of alight-colored inert filler material, said Alayer -beingsubstantiallyfree of polymerizable material, adhered directly to said rst layer asecond layer of a mixture of from about 6 to 12 parts of cellulosenitrate per part of polyvinyl acetate, and a gelatino-silver halideemulsion layer adhered to said second layer by means of a gelatin layer.

9. A light-sensitive photographic element comprising a metal support,adhered directly thereto, a rst layer of a mixture of approximatelyequal parts by weight of polyvinyl acetate and a resinous copolymercontaining about 86% by weight of vinyl chloride groups, about 13% byweight of vinyl acetate groups and about;1% by weight of maleic acidgroups together with from about 25-75% by weight of resin of alight-colored inert filler material, said layer being substantially freeof polymerizable material, adhered directly to said rst layer a secondlayer of a mixture of from about 6 to 12 parts of cellulose nitrate perpart of polyvinyl acetate, a third layer of a mixture of from about 2 to6 parts of partially hydrolyzed polyvinyl acetate per part cellulosenitrate adhered directly to said second layer, and a polyvinylalcohol-silver halide emulsion layer adhered to said third layer bymeans of a layer of polyvinyl alcohol.

10. A light-sensitive photographic element comprising a metal support,adhered directly thereto, a rst layer of a mixture of approximatelyequal parts by weight of poly- 25 vinyl acetate and a resinous copolymercontaining about 86% by weight of vinyl chloride groups, about 13% byweight of vinyl acetate groups and about 1% by weight of maleic acidgroups together with from about 25-75% by weight of resin of alight-colored inert ller material, said layer being substantially freeof polymerizable material, adhered directly to said first layer a secondlayer of a mixture of from about 6 to 12 parts of cellulose nitrate perpart of polyvinyl acetate, and a hydrophilic cellulose organic acidester-silver halide emulsion layer adhered to said second layer by meansof a layer of hydrolyzed cellulose organic acid ester of approximately19 to 33% acyl content. i

References Cited in the tile of this patent UNITED STATES PATENTS NumberName Date 2,362,580 Nadeau et al Nov. 14, 1944 2,398,056 Staud Apr. 9,1946 2,411,590 Powell Nov. 26, 1946 2,483,465 Johnson Oct. 4, 19492,527,263 Hart Oct. 24, 1950 2,569,954 Ruebensaal Oct. 2, 1951 FOREIGNPATENTS Number Country Date 600,039 Great Britain Mar. 30, 1948

1. A LIGHT-SENSITIVE PHOTOGRAPHIC ELEMENT COMPRISING A METAL SUPPORT,ADHERED DIRECTLY THERETO, A FIRST LAYER OF A MIXTURE OF A LIGHT-COLOREDINERT FILLER MATERIAL AND A RESINOUS COPOLYMER OF A MIXTURE OF VINYLCHLORIDE, VINYL ACETATE AND AN A,B-ETHYLENICALLY UNSATURATEDDICARBOXYLIC ACID, SAID LAYER BEING SUBSTANTIALLY FREE OF POLYMERIZABLEMATERIAL ADHERED DIRECTLY TO SAID FIRST LAYER A SECOND LAYER OF AMIXTURE OF POLYVINYL ACETATE AND CELLULOSE NITRATE, AND A HYDROPHILICORGANIC COLLOID-SILVER HALIDE EMULSION LAYER ADHERED TO SAID SECONDLAYER.